Blends of epoxy resins and acrylonitrile butadiene-styrene graft copolymers



United States Patent US. Cl. 260-836 7 Claims ABSTRACT OF THE DISCLOSUREAn epoxy resin-ABS graft polymer blend composition. The blend iscomprised of a range of between from 4-96 parts by weight of epoxy resinwith correspondingly 96-4 parts by weight ABS graft polymer. The blendis useful for adhesives, coatings, films, fibers and the like.

Background Prior to this invention, epoxy resins were utilized in agreat variety of adhesive and coating applications which required hightemperature resistance combined with good adhesive strength. It was wellknown, however, that the epoxy resins were relatively brittle materialswhen cured and exhibited comparatively poor impact strength andflexibility when used in films and coatings. These qualities made epoxyresin difficult, and in many cases, impossible, to use in applicationswhich required flexibility.

It has been found that new and useful compositions may be prepared byblending epoxy resins with ABS graft polymers. These blends have beenfound useful for a variety of applications such as films, fibers,adhesives, coatings, and the like. The compositions have also been foundto be extraordinarily effective adhesives and coatings for metals, Wood,plastics, including plated plastics, leather and the like.

Summary of invention Generally stated, this invention is directed tocompositions prepared by blending from about 4 parts by weight of epoxyresin to about 96 parts by weight epoxy resin with correspondingly fromabout 96 parts by weight graft polymer to about 4 parts by weight graftpolymer.

The compositions prepared in accordance with this invention combinechemical resistance and good adhesion (when used as adhesives) withextraordinary flexibility, shear strength, and impact characteristics.The compositions of this invention may be cured in situ either with orwithout heat in the presence of a curing agent.

It will be noted that the greater the epoxy resin content in the blend,the harder and more brittle will be the compositions. Also, as the epoxycontent is increased in the blends, chemical resistance and hightemperature strength will increase. As the amount of the graft polymeris increased in the compositions, the flexibility and impact strengthsof the compositions will increase. Thus, by merely varying the relativeratios of the two components in the blends, extraordinary adhesives andcoating compositions may be prepared as well as flexible films andfibers.

The specific epoxy resins utilized in this invention are normallyprepared by reacting an epoxide containing compound such asepichlorohydrin with a polyhydric compound such as glycerine or abisphenol in the presence of sufiicient basic material to bind thehydrochloric acid to form epoxy terminated prepolymers. Epoxies may alsobe prepared by epoxidation of polyolefins with a peroxidizing agent suchas peracetic acid. The resins formed vary according to the molarproportions and reaction conditions and have melting points ranging fromabout 0 C. to about C. and a molecular weight between about 300 and4000. There are a great variety of epoxy resins which are availablecommercially in a wide range of epoxy content, molecular weight,softening point and compositions. For example, it has been found thataliphatic epoxy resins such as Epon 812, a triglycidyl ether of glycerolhaving an epoxy equivalent of 140-160 and a viscosity in centipoises at25 C. of 100-170, aromatic epoxies such as DEN 438 a polyglycidyl etherof phenol-formaldehyde novolac having an epoxy equivalent weight of176-181 and a viscosity at 52 C. of 35,000-70,000 centipoises, or Epon828 may be used as well as modified epoxy resins such as Epon 815, Epon828 diluted with 11% butyl glycidyl ether having an epoxy equivalentweight to and a viscosity of 500-700 centipoises at 25 C. The modifiedepoxies utilized may be blended with either a second epoxy, aplasticizer or the like. The specific epoxy resins utilized in theadhesive examples set forth in this invention were Epon 828, abisphenol-Aepichlorohydrin liquid resin having a molecular weight ofabout 380, and Unox 221, an epoxy prepared by epoxidation of apolyolefin with peracetic acid.

The graft polymers utilized in this invention are commonly known as ABSgraft polymers. A graft polymer is a polymer prepared by firstpolymerizing a monomer (or mixture of monomers) with subsequentpolymerization of a second monomer or group of monomers onto the productof the first polymerization. The first polymerization prepares what ishereinafter referred to as the rubbery backbone.

The specific graft polymers utilized in this invention are prepared byfirst polymerizing a conjugated diene, such as butadiene, or aconjugated diene in the presence of a monovinyl aromatic hydrocarbonsuch as styrene, to provide a polymerized diene rubbery backbone such aspolybutadiene or a butadiene-styrene copolymer backbone. Thereafter, asecond monomer or group of monomers are grafted onto the rubberybackbone to complete the graft polymer. This is accomplished by theaddition and interaction under polymerization conditions of anacrylonitrile, substituted acrylonitrile, or an acrylic acid ester and amonovinyl aromatic hydrocarbon exemplified respectively by acrylonitrileor methyl methacrylate and styrene.

The backbone, i.e., conjugated diene polymer or copolymer, is preparedso as to comprise from about 60 percent to about 10 percent by weight ofthe total composition and the acrylonitrile, substituted acrylonitrileor acrylic acid ester and the monovinyl aromatic hydrocarbon that ispolymerized in the presence of the backbone polymer or copolymercomprises from about 40 percent to about 90 percent by Weight of thetotal composition.

The acrylonitrile, substituted acrylonitrile, or acrylic acid esterpreferably comprises from about 5 percent to about 45 percent :by weightof the three-component organic mixture and the monovinyl aromatichydrocarbon comprises from about 30 percent to about 80 percent of thetotal composition. The term monovinyl aromatic hydrocarbon is meant toinclude compounds such as styrene, a-rnethylstyrene, vinyltoluene,vinylxylene, ethylvinylbenzene, isopropylstyrene, chlorostyrene,dichlorostyrene, ethylchlorostyrene, mixtures thereof and the like. Theterm acrylonitrile, substituted acrylonitrile and acrylic acid estercompounds is meant to include compounds such as acrylonitrile,methacrylonitrile, ethacrylonitrile, chlo roacrylonitrile, methylmethacrylate, ethyl methacrylate, propyl methylacrylate, etc., mixturesthereof and the like.

In compounding the compositions of this invention, the ABS graft polymeris either dissolved in a solvent or mixed with the epoxy resin, withoutsolvent, such as on a rubber mill. The two primary components arenormally placed in 3 4 solution by adding them to a solvent. Prior toutilization of polybutadiene. The graft polymer of the examples of thecomposition as a film, fiber, adhesive, coating, etc., designated asGraft Copolymer B was prepared from a curing agent is added. It shouldbe understood that a about 29 parts by weight of acrylonitrile and 58parts by solvent lowers the solids content and if 100 percent solidsweight of styrene polymerized in the presence of about are desired, thesolvent may be eliminated. Solvents that 5 13 parts by weight ofpolybutadiene. The graft polymer may be used, if a solvent is desired,are those in which designated as C was prepared from 39 parts by weightof both the epoxy resin and ABS graft polymer are soluble. methylmethacrylate and 38 parts by weight of styrene Solvents such as methylethyl ketone, cyclohexanone, polymerized in the presence of a -90rubbery copolyacetone, methyl isobutyl ketone, toluene and xylene havemer of styrene-butadiene. As mentioned, other monomers been founduseful. Solvents are used primarily to facilitate 10 may be substitutedto prepare the graft polymers, e.g., handling and when utilized, areallowed to evaporate prior other monovinyl aromatic hydrocarbons may besubstito bonding. tuted for styrene and other acrylic acid nitriles forthe In the curing of the compositions, a reactive crossacrylonitrile anda styrene-butadiene substrate may be linking agent is utilized tocrosslink the compositions, and substituted for the polybutadiene.

heat is applied as set forth in the tables. Crosslinking 15 Thecompositions utilized in the examples were comagents such aspolyarnines, e.g., triethylenetetramine, pounded by mixing the graftpolymer and the designated boron trifluorideamine complex, dibasic acidanhydride, epoxy resin in a methyl ethyl ketone solvent in thepressubstituted imidazoles, phenolics, and substituted phenol ence of 10parts by weight curing agent. The epoxy resins catalysts, and urearesins have been found to be suitable. that are illustrated in theexamples are Epon 828 (epoxy) The curing agent may be present in amountsfrom about a low molecular weight epoxy resin sold by Shell Chemonepercent by weight to about ninety percent by weight ical and Unox 221,an epoxy resin prepared by peroxidaof the total composition dependingupon the specific curtion of polyolefin by peracidic acid sold by UnionCaring agent and epoxy resin being utilized. Lewis acid curing bide,however, other Shell epoxy resins such as Epon agents, such as stannouschloride and boron trifluoride re- 1009, 1001, 1004, 1045-A-80, 1031, atetrafunctional quire relatively low amounts, i.e., from about one toabout solid polyglycidyl ether of tetraphenylene ethane having an fivepercent, whereas the amine complexes may require epoxy equivalent weightof 210-240, 812 and 1002, as

from four to fifteen percent and the carboxylated materiwell as Cibaepoxy resins such as 6005, ECN 1235, EPN als, e.g., carboxy terminatedbutadiene and methacrylic 1139', ECN 1299, 6010 and the like may also beused. The acid, as well as polyamides, such as those prepared bypreferred molecular weight epoxy resins are those having condensation ofpolymerized unsaturated acid with dia molecular weight between about 300to 4000.

COMPOSITION OF EPOXY RESIN Epoxy Equivalent Name Wt. Molecular Wt.Viscosity (eentipoises) Chemical Composition Epon 828 185-192 Doubleepoxy equivalent 10,00016,000 at 25 0 Liquid DGEBA.* Epon 1009.- 2,500-4, 000 do 145-155 at 25 C- Solid D GEBA. Epon 1001-- 450-550 do65-75 at 25 C Do. Epon 1004 875-1, 025 do 95-105 at 25 C Do. Epon 1002.-600-700 d0 75-85 at 25 C Do. Ciba 6005 182-189 dO WOO-10,000 at 25 CLiquid DGEBA. ECN 1235 215 Several times epoxy equivalent at 25 CPolyglycidyl ether of orthocresol-formalwt. dehyde novolac resin. EPN1139 172479 ..---d0 1700 at 52 C Polyglycidyl ether phenol-formaldehydenovolac resin. ECN 1299 235 d0 99 at 25 C Polyglycidyl ether oforthocresol-fonnaldehyde novolac resin. 010 185196 Double epoxyequivalent l2,000-16,000 at 25 C Liquid D GEBA. Unox 221 252- 1Dicyclodiepoxy carboxylate.

Sp. gravity, 1.750; B.P., 354 0.; Flash point, 400 C.

*1) GE BA-diglycidyl ether of bisphenol A resin. amines, require as muchas fifty to ninety percent by The results of the preparation of variouscomposiweight. The higher concentrations of curing agent appear tronsare set forth in the tables which show the physical to enhance theflexibility and temperature res1stance of properties of the graftpolymer-epoxy blends. the resulting compositions. In preparing theadhesives set forth in the tables, vari- T he compositions of thisinvention may utihze fillers ous proportions of epoxy resin wereutilized in conand pigments, such as titanium dioxide, zinc oxide,silica, junction with varying proportions of graft polymer. For alumina,nickel oxide, lead oxide and the like, and in purposes of illustration,the amount of epoxy resin varied many cases, the fillers and plgmentsimpart strength as from about 4 percent to about 96 percent of the totalwell as color to the compositions. composition, and correspondingly, thegraft polymer As mentioned, the compositions of this invention arevaried from about 96 percent to about 4 percent of the useful as filmsand fibers and are especially useful as totalcompositiom coatings and asadhesives. The examples set forth the I th testing of th dh si o itiASTM strength pr per i f Specific fiompositiims that are ulil- TestD-1002-64 was utilized. Specifically, in the testing lzed m adheringvarious materials to each other. The exof adhesion of steel to steel, 4"x 7" steel strips were amples also show the strength of the compositionsas applied i h an dh i urf f /2" X 7" along ne coatings. Thecompositions of this invention may also be edge, f the strip and theplates were applied to one anused in adhering flock ABS Suffaces, WoodSurfaces, other along that surface having adhesive applied thereto.fabric, concrete, ceramics, steel, etc., and are especially Mi i l ipressure was li d along h over. useful in adhering materials tochrome-plated ABS sur- 65 l d ti f th strips, Th trips were l d i nfaCBS- Most Of the examples Set forth the Physical EP P- oven for theindicated time and temperature shown in fifties and CHTi1 1gtemperaturesfind me Of the O P the table. After the oven cure, thestrips were condit o s W utllizfld as adhesl'ves, however, it will betioned for twenty-four hours in a constant temperature, understood thatthe curing period as well as the relative constant h idi room, Th adh rd trips wer c t percentages of composition will not be greatly changed i1" x 71/ Strips d ll d t a l di t f when the materials are used ascoating compositions. 600400 i i Th average pull for the five strips TheSPeCifiC graft P y dfisignated as Graft P Y- was recorded as the valuefor the test. mer A set forth in the tables consisted of about 30 partsWh th dh i was li d as a fil h fil soup by weight acrylonitrile and 50parts by weight styrene tion was spread on a Teflon coated surface,dried at 100 polymerized in the presence of about 20 parts by weight 75F. in a vacuum oven. After the film was dried (about 3 mils thick), itwas pulled from the Teflon surface and stored for use as an adhesive.The adhesive was thereafter utilized by placing the film between thesurface to be bonded and applying pressure during the curing cycle.

In the examples, all parts are by weight unless otherwise indicated. InTable 1, the blends of this invention are used as adhesives for bondingvarious substrates such as wood, leather and steel.

TABLE 1 Parts by Adhesion of Shear, Reelpe Weight Wood top.s.l. Cure,FJtime Failure lp g 8 8 %P Y) 100 ra opo ynler A. Methyl ethyl ketone125 WOOd- 375 265 F./10 mln, wo Trlethylenetetralnln 1O lp r E6 8 (l%pv) 100 re opo ymer Methyl ethyl ketone 150 00 265 F-IIO min..." D0.Triethylenetetramine 10 1 2 2 8 (Epcwt ra opo ymer 75 Methyl ethylketone 175 450 265 F./10 min D Triethylenetetramine l0 Em r; g8 tliilpxw 00 re opo ymel 100 Methyl ethyl ketone 200 4 2 F./10 m1n.. Wood andbond. 'lriethylenetetralnine 10 2P i5 8 (Ep y) we re t opo ymer 133Methyl ethyl ketone 2 850 265 F./10 mln Do. Triethylenetetramine 10 ED E8 8 (F p yk 100 ra, opo ymer 200 Methyl ethyl ketone 300 7 265 F./10mm... Wood. Triethylenetetramine 10 lpg n g8 b w) 100 r t opo ymer 400Methyl ethyl ketone 500 4 2 5 F./10 mln. Do. Triethylenetetramine 10Adhesion of Leather to lpo E5 8 (l lp yk re 0 o ymer 5 Methyl ethylketone 125 Leather 75 265 F./l0 mm--. Leather. Triethylenetetramine- 10llpon g5 (l%poxy)x 100 ralt opo ymer 50 Methyl ethyl ketone 75 265 F'IIOmm Do Triethylenetetramine 10 ED i62 fP WA 3 re 1: opo ymer Methyl ethylketone 65 m D Iriethylenet etramine 10 @1 3 ig- %P Y) ra opo ymer Methylethyl ketone 175 65 minm Triethylenetetramine- 10 ee 1" l'" 123 ra opoymer Methyl ethy1ket0ne 233 65 F./ 1n-- D0. Triethylenetetramine 10 2""?t ll $88 re t opolylner Meth l ethyl ketone 30o 55 -lTriethylenetetramine. 10 2 3 t5 l k 183 L th d H P Y ea er en Methylethyl ketone 500 75 F-/10 bowl Triethylenetetramine 10 Adhesion of GCto- 5 (EP Y); ra opo ymer Methyl ethyl ketone" 500 steel 0 F-/30 mln.GC. 1 Triethylenetetramine l0 2% i l8?) ra opo ymer Methyl ethyl ketone"500 Galvanized Steel 300 190 F./30 mln Bond. Triethylenetetralnine- 10 eq l 183 raft opo yrner Methy1 ethyl ketone 500 Stalnless Steel 600 190F./30 mln G0. Triethylenetetramine. 1O E l 188 ra t opo ymer :Methylethyl ketone 500 wood- 4 0 F-/30 111111"... WOOd. Triethylenetetramine15g 400 Methyl ethyl ketone 500 Graft Copolymer 450 190 F./30 111111-...GOJ Triethylenetetramine 10 [The above five examples were repeated usingdimethylaminomethyl substituted phenol instead of triethylenetetraminewith comparable test results] Parts by Adhesion of Shear,

p.s.i. Cure, FJtilne Failure Recipe Weight G C 1 to- Epon 828 (Epoxy)100 Graft Copolyrner A. 25 Stainless Steel- 800 70 FE/Z4 hrs t. GCJMethyl ethyl ketone 800 70 FJQA hrs GtC.

D imethylaminomethylsubstltuted phenols- See footnotes at end of table.

135 Copper TABLE 1.Continued (In the following examples, the bond wassteel to steel] Parts by Adhesion of Shear, Recipe Weight Steel top.s.i. Cure, F./time Failure Epon 828 (Epoxy). Graft Copolymer A Methylethyl ketone. 125 'lriethylenetetramine l Epon 828 (Epoxy) s 100 GraftCopolymer A 50 Methyl ethyl ketone. 150 Triethylenetetramine l0 Epon 828(Epoxy). K) Graft Copolymer A 200 Methyl ethyl ketone. 300Triethylenetetramine l0 Epon 828 (Epoxy) 100 Graft Copolymer A. 400 doMethyl ethyl ketone 500 Triethylenetetrandne r 10 Epon 828 (Epoxy), 96%by wt 100 Graft Copolymer A, 4% by wt 4 Dimethylaminomethyl-substitutedphenols. 1O Methyl ethyl ketone Graft Copolymer A, 96% by wt 50 Epon 828(Epoxy) 4% by wt 2 Tnethylenetetramine 0. 2 Methyl ethyl ketone 2O GraftCopolymer A, 92.6% by wt 50 Epon 828 (Epoxy), 7.5% by wt 4'Iriethylenetetramine 0. 4 Methyl ethyl ketone. 2O Graft Copolymer A.100 Methyl ethyl ketone 200 1,650 265 F.l10min- Bond.

1, 250 265' FJIO min Do.

1, 200 265 F./l0 min D0.

1, 375 265 FJID min. Do.

1, 430 72 F./7G hrs Adhesive.

1, 140 250 I i/l8 hrs Do.

980 250 F./l8 hrs Do.

to 250 F./ 18 hrs Do.

1 Graft copolymer comprised of about 50 percent by weight styrene andpercent by weight acrylonitrile copolymerized in the presence of about20 percent by weight polybutadiene.

In Tables 2 and 3 the blends of this invention are utilized as coatingson various substrates.

l Coating of chromeplated graft copolymer specimens were tested byspraying the specimens with the recipe indicated, curing at the 200F./10 minute conditions, and allowing to stand for 24 hours at ambientconditions. Adhesive qualities were tested by drawing ten scribe marksto the inch vertically and horizontally. A strip of Scotch brand tapewas fiuni'rlilg pessed down on the scribed, coated surface and the tapewas p e o 2 In this instance, the coating failed when it pulled awayfrom the plated surface of the graft copolymer with Scotch brand tape.

3 The coating held firmly to the plated graft copolymer due to thestrength of the coating bond.

TABLE 3 Parts Shea-r, Cure Recipe by Wt. p.s.i. ./time I Epon 828(Epoxy) 100 Dlcyandiamide 4 Benzyldimethylamine. 0.2 3, 850 350l1 hr.Methyl Cellosolve 36 Methyl ethyl ketone- 100 Epon 823 (EDB Y) 10oGraitGopolymer A 400 Dicyandiamide 4 2, 200 350/ 1 hr. BenzyldimethylamO. 2 Methyl Cellosoive (applied as film) 36 Epon 828 (Epox 10 GraftCopolymer A" 25 Dicyandiamide 4 4, 350 350ll hr. Benzyldimethylamine- 0.2 Methyl ethyl ketone. 125 Epon 828 (Epoxy).-- 100 Graft Oopolymer B-400 Dicyandiamide 4 3, 120 350/1 hr. Benzyldimethylamine 0. 2 MethylCellosolve (applied as film) 36 Epon 828 (Epoxy) 100 Graft Copolymer B25 Dicyandiamide 4 4, 095 350!l hr. Bcnzyldimethylamlne- 0. 2 Methylethyl ketone 125 Unox 221 (Epoxy) 100 Borgigltrifluoride mo 4 750 2250.71 hr Methyl ethyl ketone 100 gm); 2521 (Elpoxyk, 100

ra opo ymer 400 o Boron trifluoride-monoethylamine com- 4 L850 2 250 npiex (applied as film).

Parts Shear, Cure Recipe by Wt. p.s.i. FJtime Unox 221 (Epoxy) GraftCopolymer A 25 a Boron Trifluoride-monoethylamine com- 4 3, 790 2 250 [1hr. Methyl ethyl ketone iifi h it r opo ymer o Boron Tritiuoride-m 4 5202 250 plex (applied as film). Unox 221 (Epoxy) 100 Graft Copolymer B 25U Bolion Trifluoride-znonoethyl 4 1, 600 2 250 [1 hr.

p ex. Methyl ethyl ketone 125 see 38 ra opo ymer e! Tetraethylpentamine"13 500 2 250 Methyl ethyl ketone 20 1 Measured on Steel surface.

1 Followed by 300l2 The tables illustrate the bond strengths of variouscompositions of this invention by setting forth the shear strengths ofthe bond between various exemplary materials. It will be understood bythose skilled in the art of adhesives and coatings that the bondstrengths on a given surface may be indicated for coatings as well asfor adhesives by applying the composition to a surface and measuring theshear strength. Attention is directed to Table 3 which shows that thecompositions of this invention provide stronger coating bonds onchrome-plated graft copolymer than those obtained from conventionalepoxy coatings.

The tables also indicate the strength of a graft copoly- 'mer per seadhesive is less than 100 p.s.i. if tested by the procedure set forthabove.

It will also be noted that the compositions of this invention, inaddition to being good bonding materials for steel, ceramics, Wood,fibers, leathers, etc., as Well as bonding flocks and the like tochrome-plated materials and especially chrome-plated ABS plastics, arealso useto] as films and fibers.

The compositions of this invention will find application in a variety ofuses such as adhering materials to card table tops, pool table covers,casket interiors, shoe heels, headliners for automobiles and the like.The compositions will also find application as films, encapsulatingresins, and fibers as well as coatings in the form of paints, lacquers,varnishes and the like.

It should be understood that while this invention has been described inconnection with certain specific embodiments thereof, that this is byway of illustration and not by way of limitation and the scope of theinvention is defined solely by the appended claims which should beconstrued as broadly as is consistent with the prior art.

What is claimed is:

1. A resin composition comprising from about 4% by weight to about 96%by weight of (1) an ABS graft polymer prepared by polymerizing fromabout 40-90% by weight of a mixture of monomers selected from the groupconsisting of styrene, a-rnethylstyrene, vinyltoluene, vinylxylene,ethylvinylbenzene, isopropylstyrene, chlorostyrene, dichlorostyrene,ethylchlorostyrene, acrylonitrile, methacrylonitrile, ethacrylonitrile,chloroacrylonitrile, methyl methacrylate, ethyl methacrylate, propylmethyl acrylate and mixtures thereof in the presence of from about 60%to about 10% by weight of a polymeric material selected from the groupconsisting of conjugated diene polymers and conjugated diene copolymersblended with (2) from about 96% by weight to about 4% by weight epoxyresin.

2. The composition of claim 1 wherein the composition contains fromabout one percent to about 90 percent by weight of at least one curingagent for epoxy resins selected from the group consisting of Lewis acidcuring agents, carboxylated curing agents, and polyamide, poly amine,urea, phenolic and substituted phenolic curing agents.

3. The composition of claim 1 wherein the graft polymer is prepared bypolymerizing acrylonitrile and styrene in the presence of polybutadiene.

4. The composition of claim 1 wherein the epoxy resin has a molecularweight between about 300 and 4000.

5. The composition of claim 2 wherein the curing agent is added in anamount of from about one percent to about 90 percent by weight of thetotal composition.

6. An adhesive and coating composition comprising (1) from about 4% byweight to about 96% by weight of an ABS graft polymer prepared bypolymerizing a mixture of monomers selected from the group consisting ofstyrene, a-methylstyrene, vinyltoluene, vinylxylene, ethylvinylbenzene,isopropylstyrene, chlorostyrene, dichlorostyrene, ethylchlorostyrene,acrylonitrile, methacrylonitrile, ethacrylonitrile, chloroacrylonitrile,methyl methacrylate, ethyl methacrylate, propyl methylacrylate andmixtures thereof in the presence of a polymeric material selected fromthe group consisting of conjugated diene polymers and conjugated dienecopolymers blended with (2) from about 96% by weight to about 4% byweight epoxy resin.

7. The composition of claim 1 wherein a monomer selected from the groupconsisting of acrylonitrile, methacrylonitrile, ethacrylonitrile,chloroacrylonitrile, methyl methacrylate, ethyl methacrylate and propylmethacrylate comprises from 545% by weight of the total graft polymercomposition and a monomer selected from the group consisting of styrene,a-methylstyrene, vinyltoluene, vinylxylene, ethylvinylbenzene,isopropylstyrene, chlorostyrene, dichlorostyrene and ethylchlorostyrenecomprises from about 30% to about 80% of the total graft polymercomposition and the polymeric material of the graft polymer compositioncomprises from about 10% to about 60% of the total graft polymercomposition.

References Cited UNITED STATES PATENTS 5/1967 Trementozzi 260-837 5/1967Trementozzi 260837

